EP1243688A1 - Use of chitosan nanoparticles - Google Patents

Abstract

Nanochitosans (I) are used in the production of fibers, yarns, fabrics and textile sheets. (I) are nanoparticles of chitosan. <??>An Independent claim is included for fibers, yarns, fabrics and textile sheets containing (I).

Description

Field of the Invention

The invention is in the field of textile technology and relates to its use of chitosans in a particularly finely divided form for finishing fibers, yarns, knitted fabrics, textile fabrics and textiles made therefrom.

State of the art

In contrast to most hydrocolloids, which are negatively charged in the range of biological pH values, chitosans are cationic, ie positively charged biopolymers under these conditions. The positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and personal care products and pharmaceutical preparations (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A6, Weinheim, Verlag Chemie, 1986, pp. 231-332), where they are used as moisturizers and film formers. Further overviews on this topic are also available, for example, from B. Gesslein et al. in HAPPI 27 , 57 (1990), O.Skaugrud in Drug Cosm.Ind. 148: 24 (1991) and E. Onoyen et al. in Seifen-Öle-Fette-Wwachs 117 , 633 (1991) .

Chitosans have nourishing properties, but they also have an anti-inflammatory and slightly mild biocidal, which makes them ideal for finishing textiles, preferably then when these are also cationic and therefore sensitive Occasionally, irritating plasticizers have been used. In In practice, however, the use of chitosans has so far not proven itself, because it is a fundamental one The problem is that these substances only adhere to the surface of the fibers and can be washed out quickly. The original goes accordingly Effect quickly lost.

The object of the invention was therefore to show a way in which one Textiles and their preliminary products with chitosans, if not permanently, at least so can equip for a significantly longer period of time, so that the wearer can Series of washes and when using fabric softener still enjoy the care and anti-inflammatory properties of chitosan.

Description of the invention

The invention relates to the use of nanochitosans for the production of fibers, Yarns, knits and fabrics in which they are used in quantities from 0.01 to 1, preferably 0.05 to 0.5 wt .-% - based on the dry weight - be present can.

Surprisingly, it was found that the problem described at the outset is comparative can be solved easily by ensuring that Chitosane are used, which differ from the products of the prior art have small average particle diameters that they are not on the surface of the fibers stick, but are stored between the fibrils, where they are difficult to access are and cannot be removed as quickly.

Chitosans and chitosan derivatives

Chitosans are biopolymers and belong to the group of hydrocolloids. Chemically speaking, these are partially deacetylated chitins of different molecular weights, which contain the following - idealized - monomer unit:

The production of chitosans is based on chitin, preferably the shell remains of crustaceans, which are available in large quantities as cheap raw materials. The chitin is used in a process that was first developed by Hackmann et al. has been described, usually first deproteinized by adding bases, demineralized by adding mineral acids and finally deacetylated by adding strong bases, it being possible for the molecular weights to be distributed over a broad spectrum. Appropriate methods are, for example, made from Makromol. Chem. 177 , 3589 (1976) or French patent application FR 2701266 A1 . Such types are preferably used, as are disclosed in German patent applications DE 4442987 A1 and DE 19537001 A1 (Henkel), and which have an average molecular weight of 800,000 to 1,200,000 Daltons, a viscosity according to Brookfield (1% by weight in Glycolic acid) below 5000 mPas, a degree of deacetylation in the range from 80 to 88% and an ash content of less than 0.3% by weight. In addition to the chitosans as typical cationic biopolymers, anionically, nonionically or cationically derivatized chitosans, such as carboxylation, succinylation, alkoxylation or quaternization products, as described, for example, in German patent DE 3713099 C2 (L'Oréal ) and the German patent application DE 19604180 A1 (Henkel).

Production of nanochitosans by spray drying and evaporation

Nanochitosans are to be understood as approximately spherical solids, some average diameter in the range of 10 to 300, preferably 50 to 200 and in particular Have 100 to 150 nm. A particularly simple process for producing the nanochitosans is the spray drying of chitosan solutions in water and / or organic Solvents, such as alcohols or (hydroxy) carboxylic acids. typically, spray drying takes place at temperatures in the range from 100 to 110 ° C. and pressures from 10 to 100 mbar.

Another suitable method for producing the nanoscale particles is offered by the evaporation technology, which has parallels with conventional spray drying. in this connection the starting materials are first in a suitable organic solvent (e.g. Alkanes, vegetable oils, ethers, esters, ketones, acetals and the like) dissolved. Subsequently the solutions are so in water or other non-solvent, if necessary in the presence of a surfactant dissolved therein that there is by homogenizing the two immiscible solvents into one Precipitation of the nanoparticles occurs, the organic solvent preferably evaporating. Instead of an aqueous solution, O / W emulsions or O / W microemulsions can also be used be used.

Production of nanochitosans using the RESS process

(a) die Ausgangsstoffe unter überkritischen oder nahekritischen Bedingungen in einem geeigneten Lösungsmittel löst,

(b) die fluide Mischung über eine Düse in ein Vakuum, ein Gas oder eine Flüssigkeit entspannt, und

(c) das Lösemittel dabei gleichzeitig verdampft.

However, the production of the nanoparticles by rapid relaxation of supercritical solutions (Rapid Expansion of Supercritical Solutions RESS) is more advantageous, for example from the article by S.Chihlar, M.Türk and K. Schaber in Proceedings World Congress on Particle Technology 3, Brighton, 1998 is known and leads to a particularly homogeneous distribution of the size diameter. In a preferred embodiment of the invention, nanoscale chitosans and / or chitosan derivatives are used, which are obtained by

(a) dissolving the starting materials in a suitable solvent under supercritical or near-critical conditions,

(b) the fluid mixture is expanded into a vacuum, gas or liquid via a nozzle, and

(c) the solvent evaporates at the same time.

In order to prevent the nanoparticles from caking again, it is recommended to use the To dissolve starting materials in the presence of suitable protective colloids or emulsifiers and / or the critical solutions in aqueous and / or alcoholic solutions of the protective colloids or Relax emulsifiers or in cosmetic oils, which in turn are dissolved again May contain emulsifiers and / or protective colloids. Suitable protective colloids are included e.g. Gelatin, casein, gum arabic, lysalbic acid, starch and polymers such as Polyvinyl alcohols, polyvinyl pyrrolidones, polyalkylene glycols and polyacrylates.

Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/ oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen, an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe sowie Alkylamine mit 8 bis 22 Kohlenstoffatomen im Alkylrest;

Alkyl- und/oder Alkenyloligoglykoside mit 8 bis 22 Kohlenstoffatomen im Alk(en)ylrest und deren ethoxylierte Analoga;

Anlagerungsprodukte von 1 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;

Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;

Partialester von Glycerin und/oder Sorbitan mit ungesättigten, linearen oder gesättigten, verzweigten Fettsäuren mit 12 bis 22 Kohlenstoffatomen und/oder Hydroxycarbonsäuren mit 3 bis 18 Kohlenstoffatomen sowie deren Addukte mit 1 bis 30 Mol Ethylenoxid;

Partialester von Polyglycerin (durchschnittlicher Eigenkondensationsgrad 2 bis 8), Polyethylenglycol (Molekulargewicht 400 bis 5000), Trimethylolpropan, Pentaerythrit, Zuckeralkoholen (z.B. Sorbit), Alkylglucosiden (z.B. Methylglucosid, Butylglucosid, Laurylglucosid) sowie Polyglucosiden (z.B. Cellulose) mit gesättigten und/oder ungesättigten, linearen oder verzweigten Fettsäuren mit 12 bis 22 Kohlenstoffatomen und/oder Hydroxycarbonsäuren mit 3 bis 18 Kohlenstoffatomen sowie deren Addukte mit 1 bis 30 Mol Ethylenoxid;

Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol gemäß DE 1165574 PS und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, Methylglucose und Polyolen, vorzugsweise Glycerin oder Polyglycerin.

Mono-, Di- und Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEG-alkylphosphate und deren Salze;

Wollwachsalkohole;

Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;

Block-Copolymere z.B. Polyethylenglycol-30 Dipolyhydroxystearate;

Polymeremulgatoren, z.B. Pemulen-Typen (TR-1,TR-2) von Goodrich;

Polyalkylenglycole sowie

Glycerincarbonat.

Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms, with alkylphenols with 8 to 15 carbon atoms in the alkyl group and alkylamines with 8 to 22 carbon atoms in the alkyl radical;

Alkyl and / or alkenyl oligoglycosides with 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs;

Addition products of 1 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;

Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;

Partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated, branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 mol ethylene oxide;

Partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosaturated (e.g. cellulose) or unsaturated (e.g. cellulose) , linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;

Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE 1165574 PS and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol.

Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

Lanolin alcohol;

Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

Block copolymers, for example polyethylene glycol 30 dipolyhydroxystearate;

Polymer emulsifiers, for example Pemulen types (TR-1, TR-2) from Goodrich;

Polyalkylene glycols as well

Glycerol carbonate.

Ethylene Oxide

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are mixtures of homologs whose average degree of alkoxylation is the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out. C _12/18 fatty acid _monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE 2024051 PS as refatting agents for cosmetic preparations.

Alkyl and / or alkenyl oligoglycosides

Alkyl and / or alkenyl oligoglycosides, their preparation and their use are out known in the art. They are manufactured in particular through implementation of glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. Regarding the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically bound to the fatty alcohol, as well as oligomeric Glycosides with a degree of oligomerization of up to preferably about 8 are suitable. The degree of oligomerization is a statistical mean, one for such technical products are based on the usual homolog distribution.

partial glycerides

Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, Hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, Oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid moglyceride, ricinoleic acid diglyceride, Linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, Erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, Tartaric acid diglyceride, citric acid monoglyceride, citric diglyceride, malic acid monoglyceride, Malic acid diglyceride and their technical mixtures, the subordinate may still contain small amounts of triglyceride from the manufacturing process. Likewise Addition products of 1 to 30, preferably 5 to 10, mol ethylene oxide are suitable to the partial glycerides mentioned.

sorbitan

Sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, Sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, Sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucate, Sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquicinoleate, sorbitan diricinoleate, Sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, Sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, Sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, Sorbitan citrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan maleate, Sorbitan trimaleate and their technical mixtures. Are also suitable Addition products of 1 to 30, preferably 5 to 10, moles of ethylene oxide to the above Sorbitan.

polyglycerol

Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearates (Dehymuls® PGPH), polyglycerol-3-diisostearate (Lameform® TGI), polyglyceryl-4 Isostearate (Isolan® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (Isolan® PDI), polyglyceryl-3 methylglucose distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate isostearates and their mixtures. Examples of other suitable polyol esters are the mono-, di- and optionally reacted with 1 to 30 mol ethylene oxide Triester of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, Tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like.

Anionic emulsifiers

Typical anionic emulsifiers are aliphatic fatty acids with 12 to 22 carbon atoms, such as palmitic acid, stearic acid or behenic acid, and dicarboxylic acids with 12 to 22 carbon atoms, such as azelaic acid or Sebacic acid.

Amphoteric and cationic emulsifiers

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example the cocoacylaminopropyidimethylammoniumglycinate, and 2-alkyl-3-carboxylm -hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C _8/18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkylaminopropionate, coconut acylaminoethylaminopropionate and C _12/18 acyl sarcosine. Finally, cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred

The preferred nanoscale chitosans or chitosan derivatives to be used are which are encased in a protective colloid and / or an emulsifier. Usually the protective colloids or emulsifiers in amounts of 0.1 to 20, preferably 5 to 15 wt .-% - based on the chitosans and / or chitosan derivatives - used.

Production of nanochitosans by GAS, PCA or PGSS processes

Another possibility for the production of nanoparticles is the so-called GAS process (Gas Anti Solvent Recrystallization). The process uses a highly compressed Gas or supercritical fluid (e.g. carbon dioxide) as a non-solvent for crystallization of solutes. The compressed gas phase is in the primary solution of the starting materials initiated and absorbed there, which increases the liquid volume, the solubility decreases and fine particles are excreted.

The PCA method (Precipitation with a Compressed Fluid Anti-Solvent) is similarly suitable. Here the primary solution of the starting materials is introduced into a supercritical fluid, whereby finely divided droplets form in which diffusion processes take place, so that a The finest particles are precipitated.

In the PGSS process (Particles from Gas Saturated Solutions), the starting materials melted by injecting gas (e.g. carbon dioxide or propane). Pressure and Temperatures reach near or supercritical conditions. The gas phase dissolves in Solid and causes a reduction in the melting temperature, viscosity and surface tension. When expanding through a nozzle, there are cooling effects to form the finest particles.

textiles

The invention further relates to fibers, yarns, knitted fabrics and textile fabrics, including consumer end products as well as textiles using of these precursors have been produced and nanochitosans, preferably in Amounts of 0.01 to 1 and in particular 0.05 to 0.5 wt .-% - based on the dry weight - contain. The finishing of finished textiles, for example, can by impregnation in the immersion bath and subsequent drying. In the same way fibers and yarns can also be finished by using the nanochitosans for example as components of winding oils or spin fiber preparations.

Examples

To produce the nanoscale chitosans and chitosan derivatives (Examples 1 to 5) , carbon dioxide was first taken from a reservoir at a constant pressure of 60 bar and cleaned over a column with an activated carbon and a molecular sieve packing. After liquefaction, the CO _{2 was} compressed to the desired supercritical pressure p using a diaphragm pump at a constant flow rate of 3.5 l / h. The solvent was then brought to the required temperature T1 in a preheater and passed into an extraction column (steel, 400 ml) which was loaded with the chitosan or chitosan derivative. The resulting supercritical, ie fluid, mixture was sprayed through a laser-drawn nozzle (length 830 μm, diameter 45 μm) at a temperature T2 into a plexiglass expansion chamber which contained a 4% by weight aqueous solution of an emulsifier or protective colloid. The fluid medium evaporated and the dispersed nanoparticles enclosed in the protective colloid remained. To produce the nanoparticles according to Example 6 , a 1% by weight solution of chitosan in glycolic acid was added dropwise to a 4% by weight aqueous solution of Coco Glucosides with vigorous stirring at 40 ° C. and a reduced pressure of 40 mbar. The evaporating solvent was condensed in a cold trap while the dispersion with the nanoparticles remained. The process conditions and the mean particle size range (determined photometrically by the 3-WEM method) are given in Table 1 below. nanoparticles E.g. Chitosan (derivative) Solv. p bar T1 ° C T2 ° C Emulsifier / protective colloid PGB nm 1 chitosan CO ₂ 200 80 175 polyvinyl alcohol 50-125 2 chitosan CO ₂ 180 70 160 Polyethylene glycol (M = 400) 70-130 3 chitosan ** CO ₂ 200 85 180 polyvinyl alcohol 70-140 4 Chitosan succinate * ** CO ₂ 200 85 175 polyvinyl alcohol 50-150 5 chitosan * CO ₂ 200 85 175 Coco Glucosides 50-150 6 chitosan * * - - - - Coco Glucosides 65-140

Application engineering examples. 100 g of polyester fabric was impregnated three times at 25 ° C. over a period of 20 min each with a 5% by weight aqueous solution of (a) nanochitosan according to Example 1 and (b) conventional chitosan powder (Hydagen® DCMF, Cognis Deutschland GmbH) and then dried. The fabrics were then also washed three times in a launder-o-meter with a commercially available liquid mild detergent (30 ° C., 16 ° dH) and the content of chitosan in the wash liquors was determined by HPLC. The chitosan content for the first wash was set at 100% using the comparative product for all other tests. The washed tissues were incinerated and the relative chitosan content was determined via the amount of nitrogen compared to an untreated tissue (= 100%). The results are summarized in Table 2. Washing attempts and chitosan contents (figures in% rel.) untreated treated with nanochitosan treated with conventional chitosan Chitosan wash liquor - after 1st wash 0 5 100 - after 2nd wash 0 5 80 - after 3rd wash 0 4 1 Chitosan tissue 100 103 100

The tests show that in the case of the fabric equipped according to the invention per wash cycle only a maximum of 5% of the chitosan can be removed (decreasing tendency) while in use of conventional chitosan practically no chitosan after the second wash more remains on the fibers.

Claims (10)

Use of nanochitosans for the production of fibers, yarns, knitted fabrics and textile fabrics. Use according to claim 1, characterized in that nanochitosans with average diameters in the range from 10 to 300 nm are used. Use according to claims 1 and / or 2, characterized in that chitosans with an average molecular weight of 800,000 to 1,200,000 daltons are used. Use according to at least one of claims 1 to 3, characterized in that carboxylation, succinylation, alkoxylation or quaternization products of chitosans are used. Use according to at least one of claims 1 to 4, characterized in that nanochitosans are used which are obtained by spray drying or evaporation. Use according to at least one of claims 1 to 4, characterized in that nanochitosans are used which are obtained by the RESS process (Rapid Expansion of Supercritical Solutions). Use according to at least one of claims 1 to 4, characterized in that nanochitosans are used which are obtained by the GAS method (Gas Anti Solvent Recrystallization). Use according to at least one of claims 1 to 4, characterized in that nanochitosans are used which are obtained by the PCA process (Precipitation with a Compressed Fluid Anti-Solvent). Use according to at least one of claims 1 to 4, characterized in that nanochitosans are used which are obtained by the PGSS process (Particles from Gas Saturated Solutions). Fibers, yarns, knitted fabrics and textile fabrics contain nanochitosans.